KR20130078741A - Flame retardant thermoplastic resin composition and article fabricated using the same - Google Patents

Abstract

PURPOSE: A flame retardant thermoplastic resin composition is provided to include a biphenyl polyphosphate, thereby improving flame retardancy, heat resistance, impact resistance, dispersity, and transparency. CONSTITUTION: A flame retardant thermoplastic resin composition includes 100.0 parts by weight of a base resin and 0.1-30 parts by weight of a biphenyl polyphosphate represented by chemical formula 2. The base resin includes 10-99 wt% of a polycarbonate resin and 1-90 wt% of a rubber-modified aromatic vinyl-based copolymer. The weight average molecular weight of the biphenyl polyphosphate is 1,000-50,000 g/mol. The rubber-modified aromatic vinyl-based copolymer is a polymer of a rubber polymer, an aromatic vinyl-based monomer, and a monomer copolymerizable with the aromatic vinyl-based monomer.

Description

Flame retardant thermoplastic resin composition and article fabricated using the same

The present invention relates to a flame retardant thermoplastic resin composition and a molded article produced therefrom. The present invention includes a biphenyl polyphosphonate to secure flame retardancy, improve heat resistance, impact resistance, dispersibility, compatibility and transparency, and provide an environmentally friendly flame retardant thermoplastic resin composition and a molded article manufactured therefrom. .

In the alloy of polycarbonate (PC) and acrylonitrile-butadiene-styrene copolymer (ABS), PC improves impact strength and heat resistance, and ABS exhibits characteristics of improving processability and chemical resistance. As a result, the alloys of PC and ABS can be used for electronic housings because they can have better physical properties than ABS and cost reduction compared to PCs.

Flame retardancy and high heat resistance are required for use in electronics housing applications. Typically, 10% level of triphenylphosphate (TPP) in the composition may be added to obtain a V-0 level of flame retardancy. However, the problem of evaporation in the extrusion process may occur due to the low melting temperature in the TPP input.

To solve this problem, phosphorus flame retardants such as resorcinol bis (diphenylphosphate) (RDP) and bisphenol A bis (diphenylphosphate) (BDP) are used. However, when RDP or BDP-based phosphorus flame retardant is used, the heat resistance per 1 phr can be reduced by 2 ℃ and the impact resistance can also be reduced. In this case, due to the heat resistance problem, it can not be used for electronic products such as TV.

In addition, bromine-based polymer flame retardants have been recently developed for the purpose of improving heat resistance and preventing underwater ecosystem disturbance. However, the use of environmentally friendly non-halogen type flame retardants is limited.

An object of the present invention is to provide a flame retardant thermoplastic resin composition that ensures flame retardancy, and has high heat resistance and impact resistance.

Another object of the present invention is to provide an environment-friendly flame-retardant thermoplastic resin composition.

Still another object of the present invention is to provide a molded article made of the flame retardant thermoplastic resin composition.

A flame retardant thermoplastic resin composition of one aspect of the present invention comprises (A) 100 parts by weight of a basic resin comprising 10 to 99% by weight of a polycarbonate resin and (B) 1 to 90% by weight of a rubber-modified aromatic vinyl copolymer; And 0.1 to 30 parts by weight of the (C) biphenyl polyphosphonate represented by the formula (2) relative to 100 parts by weight of the base resin.

<Formula 2>

Another aspect of the present invention provides a molded article molded from the flame retardant thermoplastic resin composition.

The present invention provides a flame-retardant, high heat resistance, high impact resistance, environmentally friendly flame retardant thermoplastic resin composition and a molded article produced therefrom.

1 is 1H-NMR data of biphenyl polyphosphonate used in the examples of the present invention.

A flame retardant thermoplastic resin composition of one aspect of the present invention comprises (A) 100 parts by weight of a basic resin comprising 10 to 99% by weight of a polycarbonate resin and (B) 1 to 90% by weight of a rubber-modified aromatic vinyl copolymer; And 0.1 to 30 parts by weight of (C) biphenyl polyphosphonate based on 100 parts by weight of the base resin.

(A) Polycarbonate series  Suzy

The polycarbonate resin can be linear, branched or polyester carbonate copolymer resin and the like.

The polycarbonate resin may be prepared by melt polymerization or interfacial polycondensation of an aromatic dihydroxy compound.

In one embodiment, the polycarbonate resin may be prepared by transesterification of an aromatic dihydroxy compound represented by Formula 1 with a diaryl carbonate in the presence of a catalyst consisting of an alkali, an alkaline earth metal, or a mixture thereof.

An aromatic dihydroxy compound may be represented by the following formula (1).

&Lt; Formula 1 >

Wherein A is a single bond, C1-C5 alkylene, C5-C10 cycloalkylene, -S- or -SO2-.

Specific examples of the aromatic dihydroxy compound of the formula (1) include 4,4'-dihydroxybiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis- (4-hydroxyphenyl ) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis- (3-chloro-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane etc. are mentioned, It is not necessarily limited to this.

The diaryl carbonate can be, but is not limited to, diphenyl carbonate.

The polycarbonate-based resin may have a linear, branched or mixed form thereof. The weight average molecular weight of the polycarbonate-based resin may be 10,000-100,000 g / mol.

The polycarbonate resin may be used alone or in combination of two or more. For example, a mixture of polycarbonate resins having different flow indices may be used.

Specifically, the polycarbonate resin has a flow index of 10 to less than 50 g / 10 minutes, preferably 10 to 40 g / 10 minutes, more preferably 15 to 25 g / 10 according to ISO 1133, measured at 300 ° C. and 1.2 kg. The flow index measured at 300 ° C. and 1.2 kg according to ISO 1133 and polycarbonate-based resin (A1), which is a powder, is 50 or more and 100 or less g / 10 minutes, preferably 50 to 70 g / 10 minutes, more preferably 55 to A mixture of polycarbonate-based resin (A2) that is 65 g / 10 minutes can be used.

In the polycarbonate resin (A1) may be included in 70 to 99% by weight, (A2) in 1 to 30% by weight. Within this range, it is possible to secure flame retardancy while adjusting the viscosity and to improve heat resistance and impact resistance.

The polycarbonate-based resin may be included in 10-99% by weight, preferably 80-99% by weight, more preferably 85-95% by weight of the base resin (A) + (B). In the above range, it may be effective to increase the flame resistance and impact resistance.

(B) rubber modified aromatics Vinyl-based  Copolymer

The rubber-modified aromatic vinyl polymer is a polymer in which a rubbery polymer is dispersed in the form of particles in a matrix composed of an aromatic vinyl copolymer. It is prepared by adding and polymerizing an aromatic vinyl monomer and a vinyl monomer copolymerizable with the aromatic vinyl monomer in the presence of a rubbery polymer.

Examples of the rubber-modified aromatic vinyl polymer include acrylonitrile-butadiene-styrene copolymer resins (ABS), acrylonitrile-acryl rubber-styrene copolymer resins (AAS), acrylonitrile-ethylenepropylene rubber-styrene copolymer resins (AES) etc. are mentioned.

The rubber-modified aromatic vinyl polymer can be produced by a known polymerization method including emulsion polymerization, suspension polymerization, bulk polymerization and the like. It can be manufactured by mixing and extruding an aromatic vinyl graft copolymer alone or an aromatic vinyl graft copolymer and an aromatic vinyl copolymer to a rubbery polymer. The extrusion temperature is not limited but may be 210 ° C.

The rubber-modified aromatic vinyl polymer may be included in 1-90% by weight, preferably 1-20% by weight, more preferably 5-15% by weight of the (A) + (B) base resin.

In the rubber-modified aromatic vinyl polymer, the rubber content may be included in an amount of 5-30% by weight in the total copolymer.

The rubber-modified aromatic vinyl polymer may be composed of a rubbery polymer, an aromatic vinyl graft copolymer resin, an aromatic vinyl copolymer resin, or a mixture thereof.

The rubber-modified aromatic vinyl copolymer may include two or more aromatic vinyl graft copolymer resins, two or more aromatic vinyl copolymer resins, or a mixture thereof.

(B1) aromatic vinyl graft copolymer

The aromatic vinyl graft copolymer may be prepared by adding and polymerizing an aromatic vinyl monomer (b2) capable of graft polymerization and a monomer (b3) copolymerizable with the aromatic vinyl monomer to the rubbery polymer (b1).

Examples of the rubbery polymer (b1) include diene rubbers such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene), saturated rubbers in which hydrogen is added to the diene rubber, isoprene rubber, chloroprene rubber, and acrylic acid. Acrylic rubber such as butyl and ethylene / propylene / diene monomer terpolymer (EPDM). Preferably, polybutadiene rubber is preferable among diene rubbers.

The rubbery polymer may be included in 5-65% by weight of the aromatic vinyl graft copolymer. In preparing the aromatic vinyl graft copolymer, the average size of the rubbery particles may be 0.1 μm-4 μm, preferably 0.1 μm-1 μm in consideration of impact strength and appearance.

Aromatic vinyl monomers (b2) capable of graft polymerization to rubbery polymers include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, para-t-butylstyrene, ethyl styrene, vinyl xylene, and monochlorostyrene , Dichlorostyrene, dibromostyrene, vinyl naphthalene, and the like. Preferably styrene is preferred. The aromatic vinyl monomer (b2) may be included in 50 to 99% by weight, preferably 60 to 90% by weight, more preferably 65 to 80% by weight in (b2) + (b3).

Monomers (b3) copolymerizable with the aromatic vinyl monomers include unsaturated nitrile compounds such as saturated nitrile, acrylonitrile or methacrylonitrile, or mixtures of two or more thereof. Preferably acrylonitrile is preferred. The copolymerizable monomer (b3) may be included in 1-50% by weight, preferably 10-40% by weight, more preferably 20-35% by weight of (b2) + (b3).

The monomer (b3) copolymerizable with the aromatic vinyl monomer (b2) may be included in an amount of 35-95 wt% in the aromatic vinyl graft copolymer.

In the production of the aromatic vinyl graft copolymer, monomers such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide may be further added. These monomers can be added at 0-15% by weight in the copolymer.

(B2) aromatic vinyl copolymer

The aromatic vinyl copolymer may be prepared by polymerizing the aromatic vinyl monomer mentioned in the manufacture of the graft copolymer and a monomer copolymerizable with the aromatic vinyl monomer.

The aromatic vinyl monomers used in the aromatic vinyl copolymers include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, para-t-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, Dibromostyrene, vinyl naphthalene, and the like. Preferably styrene is preferred. The aromatic vinyl monomer is suitably 60-90% by weight of the aromatic vinyl copolymer. Preferably, it may be 70-80% by weight.

Monomers copolymerizable with the aromatic vinyl monomers include unsaturated nitrile compounds such as saturated nitrile, acrylonitrile or methacrylonitrile, or mixtures of two or more thereof. Preferably acrylonitrile is preferred. The copolymerizable monomer may be 10-40% by weight of the aromatic vinyl copolymer. Preferably it may be 20-30% by weight.

A monomer such as acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide may be further added to the aromatic vinyl copolymer for processability and heat resistance. These monomers may be added at 0-15% by weight in the aromatic vinyl copolymer.

(C) biphenyl polyphosphonate

Biphenyl polyphosphonates can be represented by the following formula (2):

<Formula 2>

Wherein R is hydrogen, a substituted or unsubstituted C1-C5 alkyl group, a substituted or unsubstituted C2-C5 alkenyl group, a substituted or unsubstituted C5-C6 cycloalkyl group, a substituted or unsubstituted C5-C6 cycloalkenyl group , A substituted or unsubstituted C6-C20 aryl group or a substituted or unsubstituted C6-C20 aryloxy group,

R1 and R2 are each independently hydrogen, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C5-C6 cycloalkyl group, a substituted or unsubstituted C6-C12 aryl group, or a halogen atom,

a and b are each independently an integer of 0 to 4,

n is an integer of 4 to 500.

In "substituted or unsubstituted" a substituent may be a hydroxy group, a C1-C5 alkyl group, a C6-C20 aryl group or a halogen.

The biphenyl polyphosphonate may be prepared by reacting a biphenol represented by the following Chemical Formula 3, a phosphonic dichloride represented by the following Chemical Formula 4, and an end capping agent in the presence of a Lewis acid catalyst.

<Formula 3>

In the above, R1 and R2 are each independently hydrogen, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C5-C6 cycloalkyl group, a substituted or unsubstituted C6-C12 aryl group or a halogen atom,

a and b are each independently an integer of 0-4.

&Lt; Formula 4 >

Wherein R is hydrogen, a substituted or unsubstituted C1-C5 alkyl group, a substituted or unsubstituted C2-C5 alkenyl group, a substituted or unsubstituted C5-C6 cycloalkyl group, a substituted or unsubstituted C5-C6 cycloalkenyl group , A substituted or unsubstituted C6-C20 aryl group or a substituted or unsubstituted C6-C20 aryloxy group.

In embodiments, the phosphonic dichloride can be added dropwise to a solution containing a biphenol, a catalyst, and an end capping agent.

4,4'-dihydroxybiphenyl may be used as the biphenol.

In one embodiment, the phosphonic dichloride may be reacted with 0.1 to 2.0 equivalents, preferably 0.5 to 1.5 equivalents, and most preferably 1 equivalent with respect to 1 equivalent of the biphenol.

The reaction of the biphenol and phosphonic dichloride can be carried out by a conventional polymerization method under a Lewis acid catalyst. Solution polymerization may be preferably used.

In an embodiment, aluminum chloride, magnesium chloride, or the like may be used as the Lewis acid catalyst, but is not necessarily limited thereto.

The Lewis acid catalyst may be applied in an amount of 0.01 to 10 equivalents, preferably 0.01 to 0.1 equivalents based on 1 equivalent of biphenol.

The reaction can also be carried out in the presence of an endcapping agent.

The end capping agent may be phenol, C1-C6 alkyl substituted phenol, C6-C10 aryl substituted phenol or mixtures thereof.

The end capping agent may be used in an amount of 1 equivalent or less, preferably 0.01 to 0.5 equivalents, based on 1 equivalent of the biphenol.

In embodiments, the reaction may be completed, followed by washing with an acid solution.

The acid solution may be applied phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, and the like, preferably phosphoric acid or hydrochloric acid. At this time, the acid solution is preferably 0.1 to 10%, preferably 5% to 10% concentration.

Thereafter, washing and filtration steps may yield biphenyl polyphosphonate in solid form. The biphenyl polyphosphonate thus prepared does not contain a bisphenol structure in the structure.

The biphenyl polyphosphonate may have a weight average molecular weight of 1,000 to 50,000 g / mol. Preferably 1,000 to 20,000 g / mol, more preferably 1,000 to 10,000 g / mol. More excellent colorability, transparency and flame retardancy can be imparted in the above range.

The biphenyl polyphosphonate may have an acid value of 0.005 to 4 KOH mg / g, preferably 0.01 to 0.05 KOH mg / g. Decomposition of the thermoplastic resin does not occur in the above range.

The biphenyl polyphosphonate may have a polydispersity index (PDI) of 1 to 3.5, preferably 1.5 to 2.5.

The biphenyl polyphosphonate does not cause decomposition of the thermoplastic resin to be mixed, and may be preferably applied as a flame retardant.

The biphenyl polyphosphonate may be included in an amount of 0.1 to 30 parts by weight, preferably 1 to 25 parts by weight, and more preferably 10 to 25 parts by weight, based on 100 parts by weight of the base resin. It is excellent in the physical properties such as flame retardancy and fluidity, impact strength, heat resistance in the above range.

The thermoplastic resin composition of the present invention may further include additives such as antioxidants, drip inhibitors, lubricants, flame retardant aids, plasticizers, heat stabilizers, drip inhibitors, compatibilizers, light stabilizers, pigments, dyes, inorganic additives, and the like. . These may be used alone or in combination of two or more. The additive may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the base resin.

The thermoplastic resin composition of the present invention can be melt-extruded in an extruder and prepared in pellet form after mixing the components and other additives simultaneously. The prepared pellets may be manufactured into various molded articles through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding.

Specimens prepared from the composition may have a thickness of 2 mm and a flame retardancy measured according to UL 94 VB regulations.

Specimens prepared with the composition may have a heat resistance (VST) of 5 kg load, 50 ° C./RH, and 3.2 mm thickness according to ISO R306 of 100 ° C. or more. Preferably, it may be 120 degreeC or more, More preferably, it is 120-140 degreeC.

Specimens prepared from the composition may have an Izod impact strength of 20 kgf.cm/cm or greater as assessed according to ASTM D256 at 1/8 "thickness. Preferably, the specimen may be 20-40 kgf.cm/cm.

Another aspect of the present invention provides a molded article molded of the thermoplastic resin composition. The molded article is excellent in impact resistance, fluidity, flame retardancy, etc. can be widely applied to parts, exterior materials, automobile parts, sundries, structural materials of electrical and electronic products.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, the following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited to the following examples. Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.

Manufacturing example  1: biphenyl Of polyphosphonates  Produce

1 equivalent of 4,4'-dihydroxybiphenyl (manufactured by Songwon Industrial Co., Ltd.), 0.3 equivalents (32.2 mol) of 4-t-butylphenol, and 0.05 equivalents (5.37 mol) of aluminum chloride (AlCl3) were 6 times higher than the biphenol input. It was added to chlorobenzene. It heated up at 131 degreeC, the reaction was started by dripping 1 equivalent of Phenylphosphonic dichloride (made by Acros). After the addition was completed, the reaction was terminated after further stirring for 2 hours. After completion of the reaction, the temperature was lowered to 80 ° C., washed with 10% aqueous hydrochloric acid solution, and then washed twice with water. Thereafter, the water layer was removed, and the final product was obtained after removing the organic layer through distillation under reduced pressure. Yield 99%. The NMR (Bruker 300MHz) data for the prepared polymer are shown in FIG. 1, and the weight average molecular weight was 4,800 g / mol, PDI was 1.9, and the acid value was 0.01 KOH mg / g (n is an integer of 4 to 500). .

Manufacturing example  2: derived from bisphenol A Of polyphosphonates  Produce

2,2-bis- (4-hydroxyphenyl) propane (100 g, 0.438 mol) was dissolved in 300 ml of methylene chloride and 152.6 ml of triethyleneamine at 25 ° C under nitrogen atmosphere. 4-dimethylaminopyridine (5.35g, 0.043mol) and 4-t-butylphenol (8.0g, 0.037mol) were added to the obtained mixed solution, dissolved, and cooled to 0 ° C. To the obtained mixed solution, a mixed solution of phenylphosphonic acid dichloride (85.4 g, 0.438 mol) and 30 ml of methylene chloride was added dropwise at 0 ° C. under nitrogen atmosphere for 1 hour. The temperature was raised to 25 ° C and stirred for 5 hours. After adding and diluting 2 L of methylene chloride, the mixture was washed with 2 L of 1N hydrochloric acid solution, and this process was repeated once. After washing with 2 L of distilled water and repeating this process twice, the methylene chloride layer was collected and concentrated under reduced pressure. Excess hexane was poured and recrystallized to obtain a white solid polymerized phosphorus compound in a yield of 92% (n is an integer of 4 to 500).

The specifications of each component used in the following examples and comparative examples are as follows.

(A) with polycarbonate resin

(A1) Polycarbonate 1: Product of Cheil Industries Co., Ltd. with flow index of 20g / 10min at 300 ℃, 1.2kg according to ISO 1133

(A2) Polycarbonate 2: A product of Cheil Industries Co., Ltd. with a flow index of 62 g / 10 min at 300 ° C and 1.2 kg according to ISO 1133.

(B) rubber-modified aromatic vinyl copolymer

(B1-1) Aromatic vinyl graft copolymer (g-ABS): Polybutadiene rubber particle diameter of 0.31 μm, polybutadiene rubber 58% by weight, sum of 71% by weight of styrene + 29% by weight of acrylonitrile 42% by weight Product of Inje Cheil Industries

(B1-2) Aromatic vinyl graft copolymer (g-ABS): Polybutadiene rubber particle diameter of 0.257 µm, Polybutadiene rubber 45% by weight, 55% by weight of styrene + 25% by weight of acrylonitrile 55% by weight Product of Inje Cheil Industries

(C) with flame retardant

(C1) Biphenyl polyphosphonate of Production Example 1

(C2) Bisphenol A-derived polyphosphonate of Production Example 2

(C3) Bisphenol A bis (diphenyl phosphate) (BDP) (Daihachi Corporation)

(D) no additives

(D1) Teflon, (D2) antioxidant (LUWAX E Powder, BASF), (D3) lubricant (IRGANOX-1076, Ciba) was used.

Example  1 to 3 and Comparative example  1-2

Each component was added according to the content of Table 1 (unit: parts by weight) and extruded at a temperature of 45 Φ and 270 ° C. in a conventional twin screw extruder to prepare pellets. After drying the pellet at 80 ℃ for 2 hours, a specimen was prepared using a 170 ton injection machine at a molding temperature of 270 ℃, mold temperature 60 ℃.

Property evaluation method

(1) Izod impact strength: A notch was made in an Izod specimen at a thickness of 3.2 mm by ASTM D256 (1/8 ", notched) and evaluated at 25 ° C.

(2) Heat resistance (VST): It measured on the conditions of 5 kg and 50 degreeC / HR by thickness 3.2mm by ISO R306.

(3) Flame retardant: Flame retardancy was measured according to the UL 94 VB flame retardant specification for the specimen of thickness 2mm.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 (A) (A1) 87 77 67 87 87 (A2) 5 15 25 5 5 (B) (B1-1) 5 5 5 5 5 (B1-2) 3 3 3 3 3 (C) (C1) 16.5 16.5 16.5 - - (C2) - - - 16.5 - (C3) - - - - 16.5 (D) (D1) 0.4 0.4 0.4 0.4 0.4 (D2) 0.3 0.3 0.3 0.3 0.3 (D3) 0.4 0.4 0.4 0.4 0.4 Impact strength
(kgf.cm/cm) 30.0 32.4 29.1 12.5 13.0 Heat resistance (℃) 129.3 129.4 129.1 97.5 98.0 Flame retardancy V-0 (22 ") V-0 (26 ") V-0 (15 ") V-0 (25 ") V-0 (24 ")

As shown in Table 1, the thermoplastic resin composition of the present invention can implement excellent impact strength and heat resistance while ensuring the same level of flame retardancy as the composition comprising the BDP (see Comparative Example 2). In addition, the thermoplastic resin composition of the present invention has an effect of maintaining high heat resistance and securing high impact compared to a composition containing bisphenol A-derived polyphosphonate (see Comparative Example 1).

Claims (12)

100 parts by weight of a basic resin containing 10 to 99% by weight of (A) polycarbonate-based resin and 1 to 90% by weight of (B) rubber-modified aromatic vinyl copolymer; And flame retardant thermoplastic resin composition comprising 0.1 to 30 parts by weight of (C) biphenyl polyphosphonate represented by the formula (2) relative to 100 parts by weight of the basic resin:
(2)

(Wherein R is hydrogen, a substituted or unsubstituted C1-C5 alkyl group, a substituted or unsubstituted C2-C5 alkenyl group, a substituted or unsubstituted C5-C6 cycloalkyl group, a substituted or unsubstituted C5-C6 cycloalke A substituted or unsubstituted C6-C20 aryl group or a substituted or unsubstituted C6-C20 aryloxy group,
R1 and R2 are each independently hydrogen, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C5-C6 cycloalkyl group, a substituted or unsubstituted C6-C12 aryl group, or a halogen atom,
a and b are each independently an integer of 0 to 4,
n is an integer from 4 to 500). The flame retardant thermoplastic resin composition of claim 1, wherein the biphenyl polyphosphonate has a weight average molecular weight of 1,000 to 50,000 g / mol. The flame retardant thermoplastic resin composition of claim 1, wherein the biphenyl polyphosphonate has an acid value of 0.005 to 4 KOH mg / g. The flame retardant thermoplastic resin composition of claim 1, wherein the biphenyl polyphosphonate has a polydispersity index (PDI) of 1 to 3.5. The method according to claim 1, wherein the polycarbonate resin is a polycarbonate-based resin (A1) having a flow index of 10 to less than 50 g / 10 min, measured at 300 ° C and 1.2 kg according to ISO 1133, and 300 ° C, according to ISO 1133. A flame-retardant thermoplastic resin composition, characterized in that the mixture is a mixture of polycarbonate-based resin (A2) having a flow index of 50 to 100 g / 10 min, measured at 1.2 kg. The flame-retardant thermoplastic resin composition according to claim 5, wherein the mixture comprises 70 to 99% by weight of (A1) and 1 to 30% by weight of (A2) in the mixture. The rubber-modified aromatic vinyl copolymer is a polymer of a rubber polymer (b1), an aromatic vinyl monomer (b2), and a monomer (b3) copolymerizable with the aromatic vinyl monomer (b2). A flame retardant thermoplastic resin composition. The method of claim 1, wherein the composition further comprises an antioxidant, anti-drip agent, lubricant, flame retardant, plasticizer, heat stabilizer, anti-drip agent, compatibilizer, light stabilizer, pigment, dye, inorganic additives or mixtures thereof. A flame retardant thermoplastic resin composition. The flame-retardant thermoplastic resin composition of claim 1, wherein the specimen prepared from the composition has a flame retardancy measured at a UL 94 VB specification and a thickness of 2 mm or more. The flame-retardant thermoplastic resin composition of claim 1, wherein the specimen prepared from the composition has a heat resistance (VST) of at least 100 ° C., evaluated at 5 kg load, 50 ° C./RH, and 3.2 mm thickness by ISO R306. The flame-retardant thermoplastic resin composition of claim 1, wherein the specimen prepared from the composition has an Izod impact strength of 20 kgf.cm/cm or greater as measured according to ASTM D256 at a thickness of 1/8 ". The molded article molded from the flame-retardant thermoplastic resin composition of any one of Claims 1-11.

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